EP1326912A1 - Polymeric films having anti-static properties - Google Patents
Polymeric films having anti-static propertiesInfo
- Publication number
- EP1326912A1 EP1326912A1 EP01924631A EP01924631A EP1326912A1 EP 1326912 A1 EP1326912 A1 EP 1326912A1 EP 01924631 A EP01924631 A EP 01924631A EP 01924631 A EP01924631 A EP 01924631A EP 1326912 A1 EP1326912 A1 EP 1326912A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- film
- inducing material
- static
- styrene
- conductivity inducing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 claims abstract description 56
- 230000001939 inductive effect Effects 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 42
- 229920002635 polyurethane Polymers 0.000 claims abstract description 14
- 239000004814 polyurethane Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 5
- 239000002174 Styrene-butadiene Substances 0.000 claims abstract description 5
- 229920001400 block copolymer Polymers 0.000 claims abstract description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000098 polyolefin Polymers 0.000 claims abstract description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 5
- 239000011115 styrene butadiene Substances 0.000 claims abstract description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 5
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims abstract description 5
- 229920006173 natural rubber latex Polymers 0.000 claims abstract 4
- 239000006185 dispersion Substances 0.000 claims description 35
- 229920000642 polymer Polymers 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000007598 dipping method Methods 0.000 claims description 20
- -1 tellarium Chemical compound 0.000 claims description 16
- 150000001450 anions Chemical class 0.000 claims description 11
- 229920003009 polyurethane dispersion Polymers 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229920006264 polyurethane film Polymers 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052789 astatine Inorganic materials 0.000 claims description 4
- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine atom Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229920001195 polyisoprene Polymers 0.000 claims description 4
- 229920005903 polyol mixture Polymers 0.000 claims description 4
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052713 technetium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 2
- 239000010408 film Substances 0.000 description 60
- 239000000203 mixture Substances 0.000 description 32
- 150000002009 diols Chemical class 0.000 description 27
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 26
- 239000004721 Polyphenylene oxide Substances 0.000 description 13
- 238000009472 formulation Methods 0.000 description 13
- 229920000570 polyether Polymers 0.000 description 13
- 239000007787 solid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 239000003945 anionic surfactant Substances 0.000 description 7
- 238000005345 coagulation Methods 0.000 description 7
- 230000015271 coagulation Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 150000001412 amines Chemical group 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 239000004970 Chain extender Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910021135 KPF6 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- WJRMGBWBIGOIOF-UHFFFAOYSA-N dodecyl benzenesulfonate;propan-2-amine Chemical compound CC(C)N.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 WJRMGBWBIGOIOF-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/017—Antistatic agents
Definitions
- This invention relates to polymeric films and gloves, and particularly to those having anti-static properties.
- a film or a glove which is anti-static For various reasons, it is desirable to provide a film or a glove which is anti-static.
- gloves worn by persons who work with or handle electronic equipment are desirably anti-static, as anti-static gloves reduce the possibility of static discharges occurring between the worker and other objects. These static discharges are often very damaging to electronic components.
- certain medical applications and clean room operations require a dust-free environment.
- the use of anti-static gloves reduces the tendency for dust and dirt to be introduced through electrostatic attraction to the wearer.
- elastomeric materials antistatic.
- topical antistatic agents such as quaternary ammonium compounds and surfactants to impart surface conductivity to polyurethane.
- these agents are quickly and easily scuffed off in applications such as shoe soles.
- conductive fillers and fibers into polyurethane, but such fillers tend to alter the physical properties and processing characteristics of the polyurethane, rendering them unsuitable for the desired applications.
- fillers can leach out of the elastomeric material or can shed as particulates. These fillers and fibers must also be used in relatively large quantities, which often makes them relatively expensive.
- JPH5-5095 describes cast elastomers comprising a halogenated alkaline earth metal salt and polyurethane.
- JPH5-5095 does not disclose films or gloves made from such composition or the process utilized to make the antistatic composition.
- U.S. Patent No. 5,677,357 there is disclosed an organic polymer composition stabilized against static comprising a polyurethane and an antistatically-effective amount of a hexahalogenated compound of the formula AMX6.
- the '357 patent describes antistatic foams, which are not necessarily suitable for gloves.
- U.S. Patent No. 5,830,541 discloses compositions stabilized against static which incorporate non- volatile metal salt conductivity inducing materials into polymers and specifically into polyurethane polymers. Such enhanced polymers are disclosed as being useful for electrostatic painting applications but not as films or gloves.
- the present invention is a process for preparing an anti-static film comprising incorporating a conductivity inducing material into a polymeric film.
- the present invention is a process for preparing an anti-static film comprising dipping a former into a polymeric dispersion to form a coated former and dipping the coated former into a solution comprising a conductivity inducing material.
- the present invention is a process for preparing an anti-static film comprising dipping a former into a polymeric dispersion to form a film on the former, stripping the film from the former, and thereafter dipping the film into a solution comprising a conductivity inducing material.
- the present invention is a process for preparing an anti-static polyurethane film comprising admixing a polyol and a conductivity inducing material to form a polyol mixture, admixing the polyol mixture with an isocyanate to form a prepolymer, dispersing the prepolymer in water to form a polyurethane dispersion, and dipping a former into the polyurethane dispersion to form the anti-static film.
- the present invention is an anti-static film comprising a polymeric film and a conductivity inducing material incorporated into the film.
- the present invention is an anti-static glove comprising a polymeric film and a conductivity inducing material incorporated in the film.
- the films and gloves of the present invention have anti-static properties and are thus suitable for, among others, medical and clean room applications.
- the polymers used to make the films of the present invention can include any polymer suitable for the desired end use.
- Such polymers include, for example, polyurethane, polyolefins, polyvinyl chloride, nitrile rubber, polyisoprene, hydrogenated block copolymers, styrene-isoprene-styrene/styrene-butadiene-styrene block copolymers, styrene butadiene latexes, and other natural rubber and synthetic latexes.
- the polymer is polyurethane.
- the polyurethane used to make the preferred films and gloves of the present invention is preferably an aqueous polyurethane dispersion.
- aqueous dispersion can be prepared by any method known to one of ordinary skill in the art of preparing polyurethane dispersions to be useful in making such dispersions subject to the following limitations.
- the process of preparing the dispersion includes at least two steps. In a first step, a prepolymer is prepared. In a subsequent step, the prepolymer is dispersed with water.
- the prepolymer can be dispersed in any way which results in a dispersion which can be used to prepare a glove having acceptable physical properties.
- the dispersions can be done by a batch process or by a continuous process. If done by a batch process, preferably, the dispersion in done by a phase inversion process wherein a small amount of water, including a small amount of anionic surfactant, is first added to a continuous prepolymer phase and mixed and then more water is added with mixing until the phase inverts.
- dispersions of the present invention are prepared by means of a continuous process, preferably they are prepared by means of a high internal phase ratio (HIPR) process.
- HIPR high internal phase ratio
- Such processes are known and are disclosed in, for Example, U.S. Patent No. 5,539,021 to Pate, et al., and WO 98/41552 Al to Jakubowski, et al.
- the resulting dispersion should have a particle size sufficient to make the dispersion stable.
- the dispersions of the present invention will have a particle size of from 0.9 to 0.05, preferably from 0.5 to 0.07 and even more preferably, from 0.4 to 0.10 microns. Most preferably, the particle size of the dispersions of the present invention is about 0.15 microns.
- the stability of the dispersion is sufficient to prevent the dispersion from coagulating under storage or shipping conditions, but not so stable that the polymer cannot be coagulated onto a substrate to prepare a film.
- Films are often prepared by methods that include thermal and chemical coagulation. During these processes, a dispersion at the surface of a substrate is destabilized and the polymer coalesces onto the substrate forming a film. If the dispersion is so stable that it cannot be readily coagulated onto the substrate, it is not useful for forming, gloves. On the other hand, if the dispersion is so unstable that it coagulates during storage or on shipping, it is also not useful for forming the gloves of the present invention.
- the polyurethane dispersions of the present invention are prepared from a nonionic polyurethane prepolymer.
- the nonionic prepolymers of the present invention are prepared with either an aliphatic or an aromatic diisocyanate.
- the diisocyanate is an aromatic diisocyanate selected from the group consisting of MDI, TDI and mixtures thereof.
- TDI can be generally used with any commonly available isomer distribution. The most commonly available TDI has an isomer distribution of 80 percent of the 2,4 isomer and 20 percent of the 2,6 isomer. For the purposes of the present invention, TDI with other isomer distributions can also be used, but often at significantly higher cost.
- MDI When MDI is used with the formulations of the present invention, it preferably has a P,P' isomer content of from 99 percent to 90 percent. Even more preferably, when MDI is used with the formulations of the present invention, it preferably has a P,P' isomer content of from 98 to 92 percent. Most preferably, when MDI is used with the formulations of the present invention, it preferably has a P,P' isomer content of about 94 percent. While MDI with such isomer distributions can be prepared by distillation during the MDI process, it can also be prepared by admixing commonly available products such as ISONATE 125M* and ISONATE 50OP*. (*ISONATE 125M and ISONATE 50OP are trade designations of The Dow Chemical Company.)
- mixtures of TDI and MDI are used to prepare the prepolymers of the present invention, they are admixed in a ratio of MDI to TDI of from 99 percent MDI to 80 percent MDI. More preferably, when mixtures of TDI and MDI are used to prepare the prepolymers of the present invention, they are admixed in a ratio of MDI to TDI of from 98 percent MDI to 90 percent MDI. Most preferably, when mixtures of TDI and MDI are used to prepare the prepolymers of the present mvention, they are admixed in a ratio of MDI to TDI of about 96 percent MDI. Preferably the prepolymers of the present invention are prepared with MDI or mixtures of MDI and TDI. Even more preferably, the prepolymers of the present invention are prepared with MDI as the only aromatic diisocyanate.
- the prepolymers of the present invention are prepared from a formulation that includes an active hydrogen containing material.
- the active hydrogen containing material is a mixture of diols.
- One component of the diol mixture is a high molecular weight polyoxypropylene diol having an ethylene oxide capping of from 0 to 25 weight percent.
- the other component of the diol mixture is a low molecular weight diol.
- the polyether diols of the formulations of the present invention can be prepared by any method known to those of ordinary skill in the art of preparing polyether polyols to be useful for preparing such diols.
- the polyether diols are prepared by the alkoxylation of a difunctional initiator in the presence of a basic catalyst.
- a polyether useful with the present invention is a product resulting from a two step alkoxylation of ethylene glycol with first propylene oxide and then ethylene oxide, in the presence of KOH as a catalyst.
- the high molecular weight polyether diol component of the diol mixture of the prepolymer formulations of present invention is preferably a polyoxypropylene diol having an ethylene oxide capping of from 0 to 25 weight percent.
- the molecular weight of this component is from 1,000 to 4,000, more preferably from 1,200 to 2,500, and most preferably from 1,800 to 2,200.
- the polyether diol is capped with from 0 to 25 percent ethylene oxide.
- the high molecular weight diol is capped with from 5 to 25 percent ethylene oxide, and more preferably, from 10 to 15 percent ethylene oxide.
- the low molecular weight diol component of some of the prepolymer formulations of the present invention can also be a product of alkoxylating a difunctional initiator.
- this component is also a polyoxypropylene diol, but it can also be a mixed ethylene oxide propylene oxide polyol, as long as at least 75 weight percent of the alkoxides used, if present, is propylene oxide.
- Diols such as propylene glycol, diethylene glycol, and dipropylene glycol can also be used with the formulations of the present invention.
- the low molecular weight diol component of the prepolymer formulations if present, has a molecular weight of from 60 to 750, preferably from 62 to 600, and most preferably, from 60 to 750, preferably from 60 to 750, preferably from 62 to 600, and most preferably, from 60 to 750, preferably from 62 to 600, and most preferably, from 60 to 750, preferably from 60 to
- the prepolymers of the present invention can be prepared in any way known to those of ordinary skill in the art of preparing polyurethane prepolymers to useful for preparing such prepolymers.
- the aromatic diisocyanate and polyether diol mixture are brought together and heated under reaction conditions sufficient to prepare a polyurethane prepolymer.
- the stoichiometry of the prepolymer formulations of the present invention is such that the diisocyanate is present in excess.
- the prepolymers of the present invention have an isocyanate content (also known as percent NCO) of from 1 to 9 weight percent, more preferably from 2 to 8 weight percent, and most preferably from 3 to 7 weight percent.
- the prepolymers of the present invention are optionally extended with a difunctional amine chain extender when the active hydrogen containing material of the prepolymer formulation is a mixture of a low molecular weight diol and a high molecular weight polyether diol.
- the difunctional amine chain extender is not optional but required when the active hydrogen containing material of the prepolymer formulation is a high molecular weight polyether diol and does not include a low molecular weight diol.
- the difunctional amine chain extender is present in the water used to make the dispersion.
- the amine chain extender can be any isocyanate reactive diamine or amine having another isocyanate reactive group and a molecular weight of from 60 to 450, but is preferably selected from the group consisting of: an aminated polyether diols; piperazine, aminoethylethanolamine, ethanolamine, ethylenediamine and mixtures thereof.
- the amine chain extender is dissolved in the water used to make the dispersion.
- the prepolymers of the present invention are nonionic. There are no ionic groups incorporated in or attached to the backbones of the prepolymers used to prepare the gloves of the present invention.
- the anionic surfactant used to prepare the dispersions of the present invention is an external stabilizer and is not incorporated into the polymer backbones of the films of the present invention.
- the prepolymers of the present invention are dispersed in water which contains a surfactant.
- the surfactant is an anionic surfactant.
- the surfactant is preferably introduced into water prior to a prepolymer being dispersed therein, but it is not outside the scope of the present invention that the surfactant and prepolymer could be introduced into the water at the same time.
- Any anionic surfactant can be used with the present invention, but preferably the anionic surfactant is selected from the group consisting of sulfonates, phophates, carboxylates.
- the anionic surfactant is sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, sodium dodecyl diphenyl oxide disulfonate, sodium n-decyl diphenyl oxide disulfonate, isopropylamine dodecylbenzenesulfonate, or sodium hexyl diphenyl oxide disulfonate, and most preferably, the anionic surfactant is sodium dodecyl benzene sulfonate.
- the dispersions of the present invention can have a solids level of from 30 weight percent to 60 weight percent. Films will not necessarily be prepared from dispersions having this level of solids. While the dispersions themselves will be stored and shipped at as high a solids content as possible to minimize storage volume and shipping costs, the dispersions can desirably be diluted prior to final use. The thickness of the film to be prepared and the method of coagulating the polymer onto a substrate will usually dictate what solids level is needed in the dispersion. When preparing films, the dispersions of the present invention can be at a weight percent solids of from 5 to 60 percent, preferably from 10 to 40 percent, and, most preferably, from 15 to 25 weight percent when preparing examination or clean room gloves. For other glove applications, the film thickness and corresponding solids content of the dispersion used can vary.
- the films of the present invention can have a tensile set of less than 5 percent.
- Other properties typically measured for examination or cleanroom applications include tensile strength and elongation.
- the tensile strength for examination or cleanroom gloves is at least 2000 pounds per square inch (psi) (13.78951 megapascal) and more preferably at least 2500 psi (17.23689 megapascal).
- the elongation for examination or cleanroom gloves is greater than 400 percent and more preferably greater than 500 percent.
- Tensile strength and elongation properties are typically measured according to ASTM D-412.
- a conductivity inducing material is incorporated into the film or glove.
- the conductivity inducing materials of the present invention are non- volatile metal salts.
- the conductivity inducing materials of the present invention will have both a cation and an anion.
- the cation of the salts can be a cation of any metal which forms an ionizable salt with one or more anions, including Li, Be, Na, Mg, Al, K, Ca, Ga, Ge, Cu, Zn, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, b, Sr, In, Sn personally Sb, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Cs, Ba, Tl, Pb, Bi, Po, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Fr, Ra and the Lanthanide series of the Periodic Table of the Elements.
- the cation is a cation of an alkali metal (Li, Na, K, Rb, Cs, Fr), an alkaline earth metal (Ca, Ba, Sr, Ra), Co, Ni, Fe, Cu, Cd, Zn, Sn, Al or Ag; more preferably the cation is a cation of Li, Na, K or mixtures thereof.
- an alkali metal Li, Na, K, Rb, Cs, Fr
- an alkaline earth metal Ca, Ba, Sr, Ra
- Co Ni, Fe
- Cu Cd, Zn, Sn, Al or Ag
- the cation is a cation of Li, Na, K or mixtures thereof.
- the anion of the non- volatile metal salt conductivity inducing material is recognizable by those skilled in the art by such characteristics as electron withdrawing groups such as halogen atoms and the possibility of resonance structures.
- the anion is preferably a relatively large, multiatomic anion having substituents like phenyl groups, sulfur atoms, and phosphorous atoms that can accept and delocalize an electron charge.
- the anion has at least one, more preferably more than one, even more preferably at least 4, most preferably at least 5, non-metallic atoms.
- Non-metallic atoms are generally considered to be selected from the group consisting of boron, carbon, silicon, phosphorous, arsenic, oxygen, sulfur, selenium, tellarium, fluorine, chlorine, bromine, iodine and astatine.
- Preferred non-metallic atoms are boron, phosphorous, sulfur, fluorine, and carbon; sulfur, phosphorous and carbon are most preferred.
- the anion is selected from a tetraphenylboron anion and a hexafluorophosphate anion.
- the amount of conductivity inducing material included in the polymer is an antistatically effective amount.
- antistatically effective amount means the amount of conductivity inducing material that is necessary to impart the required electrostatic dissipative effects to the polymeric film or glove.
- the amount of conductivity inducing material in the polymeric film or glove is 0.1 to 5.0 weight percent, more preferably 0.15 to 2.0 weight percent, and even more preferably 0.2 to 1.0 weight percent, based on the weight of the final film or glove.
- the films and gloves of the present invention have the desired properties such that they are appropriate for cleanroom applications.
- One property important in cleanroom applications is electrostatic dissipation, commonly measured by static decay time (SDT).
- SDT static decay time
- the films and gloves of the present invention have an SDT of less than 5 seconds, more preferably less than 2 seconds, and even more preferably less than 0.5 seconds, as measured according to FTMS 101B method 4046 after conditioning specimens at 12 percent relative humidity for 48 hours.
- Typical test voltages applied while measuring SDT are 1000 volts or 5000 volts, more preferably 1000 volts.
- SDT is the measured time the applied voltage is dissipated by the film or glove specimen to 10 percent of the original applied voltage.
- the films and gloves of the present invention have a surface resistivity of less than 10 ohms per square centimeter ( ⁇ /cm ), and more preferably less than 10 ⁇ /cm , measured at 12 percent relative humidity according to ANSI EOS/ESD S 11.11 test method.
- ⁇ /cm ohms per square centimeter
- the properties can vary depending upon the humidity. Electrostatic dissipation and SDT will generally be faster at a higher humidity, while resistivities will generally be lower at a higher humidity.
- the gloves of the present invention can be made self releasing by inclusion of a wax during the film forming process.
- the wax is carnauba wax. It is preferable that the wax to be used be selected from those that are not likely to induce an allergic reaction in skin that comes in contact therewith. Therefore, food grade waxes are particularly preferred for this application.
- the waxes are preferably used as an aqueous dispersion at a concentration of from 0.1 to 2 weight percent.
- additives can be included in the gloves of the present invention. Any additive which is known to those of ordinary skill in the art of preparing gloves to be useful can be used with the gloves of the present invention so long as their presence does not degrade the properties of the glove.
- the additives can also be incorporated into the gloves in any way known to be useful including, but not limited to inclusion in the prepolymer formulation and inclusion in the water used to make the dispersion.
- useful additives include titanium dioxide, calcium carbonate, silicon oxide, defoamers, biocides, and carbon particles.
- the polyurethane films used to make the gloves are advantageously applied to a hand-shaped substrate using techniques which are commonly known, such as salt coagulation, thermal coagulation, casting, and combinations thereof.
- Coagulation processes are described generally in, for example, Japanese Kokai 2/1/1990, assigned to Daiichi Kogyo Seiyaku K.K., and salt coagulation in particular is generally described in WO 96/08352, assigned to Jackson et al.
- salt coagulation also referred to herein as "dipping processes” is used to make the gloves of the present invention.
- a dipping process generally includes the steps of dipping a former into a bath containing a salt coagulant and removing the former; dipping the coagulant-coated former into a bath containing a dispersion of the desired polymer and removing the former; and stripping the resulting film from the former.
- the former will be held in air for a period of time after dipping into the polymer, in order to generate gel strength.
- the former will typically be dipped into a leaching bath such as water before it is cooled and the film is stripped from the former.
- the manner of incorporating the conductivity inducing material into the film or glove is not critical.
- the preferred method for incorporating the conductivity inducing material into the polymer will depend upon the conductivity inducing material used and the polymer used.
- the conductivity inducing material can be added during the processing of the polymer, during film formation, or by a post-treatment process.
- the conductivity inducing material can be dissolved in the polyol.
- the prepolymer is then formed such that the conductivity inducing material is solubilized in the prepolymer mixture.
- the conductivity inducing material can be added to the polyurethane dispersion after the dispersion is formed.
- a former having thereon a coagulated gel is then dipped into a solution containing the conductivity inducing material.
- a solution containing the conductivity inducing material is then dipped into a solution containing the conductivity inducing material.
- dipping preferably occurs after the leaching step but before the film is cured on the former.
- the former is soaked in the conductivity inducing material solution for from 5 to 30 seconds.
- Such dipping can be performed at room temperature, although higher temperatures can reduce the length of time needed to soak.
- the cured film is soaked in a solution containing the conductivity inducing material.
- a solution containing the conductivity inducing material can be soaked in a solution containing the conductivity inducing material.
- Such dipping can occur while the film is still on the former or after the film has been stripped from the former.
- the dipping occurs after the film has been stripped from the former, because all surfaces of the film or glove can be exposed to the salt solution.
- the length of time required to soak will depend upon the concentration of the salt solution.
- the length of time for the soak is from 1 to 10 minutes.
- the soak can be performed at room temperature, although higher temperatures can be used and in fact can reduce the amount of soak time required.
- Polyether Polyol was a 2000 molecular weight polyoxypropylene diol having 12.5 percent ethylene oxide end capping.
- Polyisocyanate A was MDI having a 4,4' isomer content of 98 percent and an isocyanate equivalent weight of 125.
- Polyisocyanate B was MDI having a 4,4' isomer content of 50 percent and an isocyanate equivalent weight of 125.
- Surfactant was 22 percent solution of sodium dodecyl benzene sulfonate in water.
- Diamine was a 230 molecular weight polyoxypropylene diamine.
- a polyurethane prepolymer was prepared by admixing 52.0 parts of Polyether Polyol, 0.33 parts STPB, and 14.7 parts of Low Molecular Weight Diol and then heating the admixture to 50°C. This material was then admixed with 33.3 parts of Polyisocyanate A which had also been warmed to 50°C. A small amount of benzoyl chloride was added to neutralize residual base in the polyols. The admixture was then heated at 70°C for 4 hours and then tested to determine NCO content. The NCO content was 5.75 percent.
- a polyurethane dispersion was prepared by admixing 200g of the prepolymer admixed with 13g water and 38g surfactant using a high shear mixer running at about 2500 rpm. Additional water was slowly added until a phase inversion was observed. Additional water was added until the solids content was 23 percent.
- a film was then prepared by a coagulation process by heating a steel plate in an oven until it reached a temperature of from 100 to 120°F (38-49°C).
- the plate was then dipped into a 20 percent solution of calcium nitrate in 1:1 by weight of water and methanol which also included about 1 wt percent of a ethoxylated octylphenol surfactant.
- the plate was then placed into an oven at 230°F (110°C) for approximately 15 minutes to form a very thin film of calcium nitate on the plate.
- the plate was allowed to cool to 105°F (40°C) and then dipped into the polyurethane dispersion diluted to 23 percent solids with deionized water and removed (total dwell time is approximately 20 sec).
- the plate was held for 5 minutes at room temperature to allow the film to generate enough gel strength, followed by leaching in a water bath at 115°F (46°C) for 10 minutes. Both sides of the plate was then sprayed with water at 115°F (40°C) for two additional minutes. The plate was then heated to 230°F (110°C) for 30 minutes and then cooled to ambient temperature. A polyurethane film was peeled from the substrate, conditioned at 12 percent relative humidity and tested for static decay time (SDT) according to Federal Test Method FTMS 101B, method 4046. Results were presented in Table I.
- Example 2 The same procedure as that described in Example 2 was followed. The film was then washed in distilled water for one hour and dried. Test results were presented in Table I.
- Example 2 Substantially the same procedure as that described in Example 2 was followed, except that the KPF6 was incorporated during film formation. After the polyurethane film had coagulated to a gel state, it was dipped into KPFfi for 1 minute, then leached for 1 minute, and then dried at 110°C for 45 minutes. Test results were presented in Table I.
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Abstract
A process for preparing an anti-static film comprising incorporating a conductivity inducing material into a polymeric film. the conductivity inducing material is a non-volatile metal salt. The polymeric film is selected from polyurethane, polyolefins, polyvinyl chloride, nitrile rubber, poylisoprene, hydrogenated block copolymers, styrene-isoprenestyre-ne/styrene-butadiene-styrene block copolymers, styrene butadiene latexes, and natural rubber latex. Anti-static films and gloves prepared from such process are also disclosed.
Description
POLYMERIC FILMS HAVING ANTI-STATIC PROPERTIES
This invention relates to polymeric films and gloves, and particularly to those having anti-static properties.
For various reasons, it is desirable to provide a film or a glove which is anti-static. For example, gloves worn by persons who work with or handle electronic equipment are desirably anti-static, as anti-static gloves reduce the possibility of static discharges occurring between the worker and other objects. These static discharges are often very damaging to electronic components. In addition, certain medical applications and clean room operations require a dust-free environment. The use of anti-static gloves reduces the tendency for dust and dirt to be introduced through electrostatic attraction to the wearer.
Several attempts have been made to render elastomeric materials antistatic. For example, it is known to use topical antistatic agents such as quaternary ammonium compounds and surfactants to impart surface conductivity to polyurethane. However, these agents are quickly and easily scuffed off in applications such as shoe soles. It is also known to incorporate conductive fillers and fibers into polyurethane, but such fillers tend to alter the physical properties and processing characteristics of the polyurethane, rendering them unsuitable for the desired applications. Moreover, fillers can leach out of the elastomeric material or can shed as particulates. These fillers and fibers must also be used in relatively large quantities, which often makes them relatively expensive.
The prior art describes some antistatic compositions that do not require the use of fillers. For example, JPH5-5095 describes cast elastomers comprising a halogenated alkaline earth metal salt and polyurethane. However, JPH5-5095 does not disclose films or gloves made from such composition or the process utilized to make the antistatic composition.
In U.S. Patent No. 5,677,357, there is disclosed an organic polymer composition stabilized against static comprising a polyurethane and an antistatically-effective amount of a hexahalogenated compound of the formula AMX6. In particular, the '357 patent describes antistatic foams, which are not necessarily suitable for gloves.
U.S. Patent No. 5,830,541 discloses compositions stabilized against static which incorporate non- volatile metal salt conductivity inducing materials into polymers and specifically into polyurethane polymers. Such enhanced polymers are disclosed as being useful for electrostatic painting applications but not as films or gloves.
It would be desirable to provide a film and, in particular a glove which has improved anti-static properties.
In one aspect, the present invention is a process for preparing an anti-static film comprising incorporating a conductivity inducing material into a polymeric film.
In a second aspect, the present invention is a process for preparing an anti-static film comprising dipping a former into a polymeric dispersion to form a coated former and dipping the coated former into a solution comprising a conductivity inducing material.
In a third aspect, the present invention is a process for preparing an anti-static film comprising dipping a former into a polymeric dispersion to form a film on the former, stripping the film from the former, and thereafter dipping the film into a solution comprising a conductivity inducing material.
In a fourth aspect, the present invention is a process for preparing an anti-static polyurethane film comprising admixing a polyol and a conductivity inducing material to form a polyol mixture, admixing the polyol mixture with an isocyanate to form a prepolymer, dispersing the prepolymer in water to form a polyurethane dispersion, and dipping a former into the polyurethane dispersion to form the anti-static film.
In a fifth aspect, the present invention is an anti-static film comprising a polymeric film and a conductivity inducing material incorporated into the film.
In a sixth aspect, the present invention is an anti-static glove comprising a polymeric film and a conductivity inducing material incorporated in the film.
The films and gloves of the present invention have anti-static properties and are thus suitable for, among others, medical and clean room applications.
The polymers used to make the films of the present invention can include any polymer suitable for the desired end use. Such polymers include, for example, polyurethane, polyolefins, polyvinyl chloride, nitrile rubber, polyisoprene, hydrogenated block copolymers, styrene-isoprene-styrene/styrene-butadiene-styrene block copolymers, styrene butadiene latexes, and other natural rubber and synthetic latexes. In a preferred embodiment, the polymer is polyurethane.
The polyurethane used to make the preferred films and gloves of the present invention is preferably an aqueous polyurethane dispersion. Such aqueous dispersion can be prepared by any method known to one of ordinary skill in the art of preparing polyurethane dispersions to be useful in making such dispersions subject to the following limitations.
The process of preparing the dispersion includes at least two steps. In a first step, a prepolymer is prepared. In a subsequent step, the prepolymer is dispersed with water.
The prepolymer can be dispersed in any way which results in a dispersion which can be used to prepare a glove having acceptable physical properties. The dispersions can be done by a batch process or by a continuous process. If done by a batch process, preferably, the dispersion in done by a phase inversion process wherein a small amount of water, including a small amount of anionic surfactant, is first added to a continuous prepolymer phase and mixed and then more water is added with mixing until the phase inverts.
When dispersions of the present invention are prepared by means of a continuous process, preferably they are prepared by means of a high internal phase ratio (HIPR) process. Such processes are known and are disclosed in, for Example, U.S. Patent No. 5,539,021 to Pate, et al., and WO 98/41552 Al to Jakubowski, et al. When prepared by either method, the resulting dispersion should have a particle size sufficient to make the dispersion stable. The dispersions of the present invention will have a particle size of from 0.9 to 0.05, preferably from 0.5 to 0.07 and even more preferably, from 0.4 to 0.10 microns. Most preferably, the particle size of the dispersions of the present invention is about 0.15 microns.
The stability of the dispersion is sufficient to prevent the dispersion from coagulating under storage or shipping conditions, but not so stable that the polymer cannot be coagulated onto a substrate to prepare a film. Films are often prepared by methods that
include thermal and chemical coagulation. During these processes, a dispersion at the surface of a substrate is destabilized and the polymer coalesces onto the substrate forming a film. If the dispersion is so stable that it cannot be readily coagulated onto the substrate, it is not useful for forming, gloves. On the other hand, if the dispersion is so unstable that it coagulates during storage or on shipping, it is also not useful for forming the gloves of the present invention.
In a preferred embodiment, the polyurethane dispersions of the present invention are prepared from a nonionic polyurethane prepolymer. The nonionic prepolymers of the present invention are prepared with either an aliphatic or an aromatic diisocyanate. Preferably, the diisocyanate is an aromatic diisocyanate selected from the group consisting of MDI, TDI and mixtures thereof. TDI can be generally used with any commonly available isomer distribution. The most commonly available TDI has an isomer distribution of 80 percent of the 2,4 isomer and 20 percent of the 2,6 isomer. For the purposes of the present invention, TDI with other isomer distributions can also be used, but often at significantly higher cost.
When MDI is used with the formulations of the present invention, it preferably has a P,P' isomer content of from 99 percent to 90 percent. Even more preferably, when MDI is used with the formulations of the present invention, it preferably has a P,P' isomer content of from 98 to 92 percent. Most preferably, when MDI is used with the formulations of the present invention, it preferably has a P,P' isomer content of about 94 percent. While MDI with such isomer distributions can be prepared by distillation during the MDI process, it can also be prepared by admixing commonly available products such as ISONATE 125M* and ISONATE 50OP*. (*ISONATE 125M and ISONATE 50OP are trade designations of The Dow Chemical Company.)
When mixtures of TDI and MDI are used to prepare the prepolymers of the present invention, they are admixed in a ratio of MDI to TDI of from 99 percent MDI to 80 percent MDI. More preferably, when mixtures of TDI and MDI are used to prepare the prepolymers of the present invention, they are admixed in a ratio of MDI to TDI of from 98 percent MDI to 90 percent MDI. Most preferably, when mixtures of TDI and MDI are used to prepare the prepolymers of the present mvention, they are admixed in a ratio of MDI to TDI of about 96 percent MDI. Preferably the prepolymers of the present invention are prepared with MDI or
mixtures of MDI and TDI. Even more preferably, the prepolymers of the present invention are prepared with MDI as the only aromatic diisocyanate.
In one embodiment of the present invention, the prepolymers of the present invention are prepared from a formulation that includes an active hydrogen containing material. In a preferred embodiment of the present invention, the active hydrogen containing material is a mixture of diols. One component of the diol mixture is a high molecular weight polyoxypropylene diol having an ethylene oxide capping of from 0 to 25 weight percent. The other component of the diol mixture is a low molecular weight diol. The polyether diols of the formulations of the present invention can be prepared by any method known to those of ordinary skill in the art of preparing polyether polyols to be useful for preparing such diols. Preferably, the polyether diols are prepared by the alkoxylation of a difunctional initiator in the presence of a basic catalyst. For example, a polyether useful with the present invention is a product resulting from a two step alkoxylation of ethylene glycol with first propylene oxide and then ethylene oxide, in the presence of KOH as a catalyst.
The high molecular weight polyether diol component of the diol mixture of the prepolymer formulations of present invention is preferably a polyoxypropylene diol having an ethylene oxide capping of from 0 to 25 weight percent. Preferably, the molecular weight of this component is from 1,000 to 4,000, more preferably from 1,200 to 2,500, and most preferably from 1,800 to 2,200. As stated, the polyether diol is capped with from 0 to 25 percent ethylene oxide. Preferably, the high molecular weight diol is capped with from 5 to 25 percent ethylene oxide, and more preferably, from 10 to 15 percent ethylene oxide.
The low molecular weight diol component of some of the prepolymer formulations of the present invention can also be a product of alkoxylating a difunctional initiator. Preferably, this component is also a polyoxypropylene diol, but it can also be a mixed ethylene oxide propylene oxide polyol, as long as at least 75 weight percent of the alkoxides used, if present, is propylene oxide. Diols such as propylene glycol, diethylene glycol, and dipropylene glycol can also be used with the formulations of the present invention. The low molecular weight diol component of the prepolymer formulations, if present, has a molecular weight of from 60 to 750, preferably from 62 to 600, and most preferably, from
125 to 500.
The prepolymers of the present invention can be prepared in any way known to those of ordinary skill in the art of preparing polyurethane prepolymers to useful for preparing such prepolymers. Preferably the aromatic diisocyanate and polyether diol mixture are brought together and heated under reaction conditions sufficient to prepare a polyurethane prepolymer. The stoichiometry of the prepolymer formulations of the present invention is such that the diisocyanate is present in excess. Preferably, the prepolymers of the present invention have an isocyanate content (also known as percent NCO) of from 1 to 9 weight percent, more preferably from 2 to 8 weight percent, and most preferably from 3 to 7 weight percent.
The prepolymers of the present invention are optionally extended with a difunctional amine chain extender when the active hydrogen containing material of the prepolymer formulation is a mixture of a low molecular weight diol and a high molecular weight polyether diol. The difunctional amine chain extender is not optional but required when the active hydrogen containing material of the prepolymer formulation is a high molecular weight polyether diol and does not include a low molecular weight diol. Preferably, the difunctional amine chain extender is present in the water used to make the dispersion. When used, the amine chain extender can be any isocyanate reactive diamine or amine having another isocyanate reactive group and a molecular weight of from 60 to 450, but is preferably selected from the group consisting of: an aminated polyether diols; piperazine, aminoethylethanolamine, ethanolamine, ethylenediamine and mixtures thereof. Preferably, the amine chain extender is dissolved in the water used to make the dispersion.
The prepolymers of the present invention are nonionic. There are no ionic groups incorporated in or attached to the backbones of the prepolymers used to prepare the gloves of the present invention. The anionic surfactant used to prepare the dispersions of the present invention is an external stabilizer and is not incorporated into the polymer backbones of the films of the present invention.
The prepolymers of the present invention are dispersed in water which contains a surfactant. Preferably the surfactant is an anionic surfactant. In the practice of preparing the dispersions of the present invention, the surfactant is preferably introduced into water prior to a prepolymer being dispersed therein, but it is not outside the scope of the present invention that the surfactant and prepolymer could be introduced into the water at the same
time. Any anionic surfactant can be used with the present invention, but preferably the anionic surfactant is selected from the group consisting of sulfonates, phophates, carboxylates. More preferably, the anionic surfactant is sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, sodium dodecyl diphenyl oxide disulfonate, sodium n-decyl diphenyl oxide disulfonate, isopropylamine dodecylbenzenesulfonate, or sodium hexyl diphenyl oxide disulfonate, and most preferably, the anionic surfactant is sodium dodecyl benzene sulfonate.
The dispersions of the present invention can have a solids level of from 30 weight percent to 60 weight percent. Films will not necessarily be prepared from dispersions having this level of solids. While the dispersions themselves will be stored and shipped at as high a solids content as possible to minimize storage volume and shipping costs, the dispersions can desirably be diluted prior to final use. The thickness of the film to be prepared and the method of coagulating the polymer onto a substrate will usually dictate what solids level is needed in the dispersion. When preparing films, the dispersions of the present invention can be at a weight percent solids of from 5 to 60 percent, preferably from 10 to 40 percent, and, most preferably, from 15 to 25 weight percent when preparing examination or clean room gloves. For other glove applications, the film thickness and corresponding solids content of the dispersion used can vary.
The desired physical properties of the glove will depend largely on the end use application. For example, for an exam glove or cleanroom application, the films of the present invention can have a tensile set of less than 5 percent. Other properties typically measured for examination or cleanroom applications include tensile strength and elongation. Preferably, the tensile strength for examination or cleanroom gloves is at least 2000 pounds per square inch (psi) (13.78951 megapascal) and more preferably at least 2500 psi (17.23689 megapascal). Preferably the elongation for examination or cleanroom gloves is greater than 400 percent and more preferably greater than 500 percent. Tensile strength and elongation properties are typically measured according to ASTM D-412.
To impart anti-static properties to the film or glove, a conductivity inducing material is incorporated into the film or glove. The conductivity inducing materials of the present invention are non- volatile metal salts. As a salt the conductivity inducing materials of the present invention will have both a cation and an anion. The cation of the salts can be a
cation of any metal which forms an ionizable salt with one or more anions, including Li, Be, Na, Mg, Al, K, Ca, Ga, Ge, Cu, Zn, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, b, Sr, In, Sn„ Sb, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Cs, Ba, Tl, Pb, Bi, Po, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Fr, Ra and the Lanthanide series of the Periodic Table of the Elements. Preferably, the cation is a cation of an alkali metal (Li, Na, K, Rb, Cs, Fr), an alkaline earth metal (Ca, Ba, Sr, Ra), Co, Ni, Fe, Cu, Cd, Zn, Sn, Al or Ag; more preferably the cation is a cation of Li, Na, K or mixtures thereof.
The anion of the non- volatile metal salt conductivity inducing material is recognizable by those skilled in the art by such characteristics as electron withdrawing groups such as halogen atoms and the possibility of resonance structures. The anion is preferably a relatively large, multiatomic anion having substituents like phenyl groups, sulfur atoms, and phosphorous atoms that can accept and delocalize an electron charge.
Preferably the anion has at least one, more preferably more than one, even more preferably at least 4, most preferably at least 5, non-metallic atoms. Non-metallic atoms are generally considered to be selected from the group consisting of boron, carbon, silicon, phosphorous, arsenic, oxygen, sulfur, selenium, tellarium, fluorine, chlorine, bromine, iodine and astatine. Preferred non-metallic atoms are boron, phosphorous, sulfur, fluorine, and carbon; sulfur, phosphorous and carbon are most preferred. Preferably, the anion is selected from a tetraphenylboron anion and a hexafluorophosphate anion.
The amount of conductivity inducing material included in the polymer is an antistatically effective amount. The term "antistatically effective amount" means the amount of conductivity inducing material that is necessary to impart the required electrostatic dissipative effects to the polymeric film or glove. Preferably, the amount of conductivity inducing material in the polymeric film or glove is 0.1 to 5.0 weight percent, more preferably 0.15 to 2.0 weight percent, and even more preferably 0.2 to 1.0 weight percent, based on the weight of the final film or glove.
Desirably, the films and gloves of the present invention have the desired properties such that they are appropriate for cleanroom applications. One property important in cleanroom applications is electrostatic dissipation, commonly measured by static decay time (SDT). Preferably, the films and gloves of the present invention have an SDT of less than 5
seconds, more preferably less than 2 seconds, and even more preferably less than 0.5 seconds, as measured according to FTMS 101B method 4046 after conditioning specimens at 12 percent relative humidity for 48 hours. Typical test voltages applied while measuring SDT are 1000 volts or 5000 volts, more preferably 1000 volts. SDT is the measured time the applied voltage is dissipated by the film or glove specimen to 10 percent of the original applied voltage.
Surface resistivity is also an important characteristic for cleanroom applications. Preferably, the films and gloves of the present invention have a surface resistivity of less than 10 ohms per square centimeter (Ω/cm ), and more preferably less than 10 Ω/cm , measured at 12 percent relative humidity according to ANSI EOS/ESD S 11.11 test method. Of course, the properties can vary depending upon the humidity. Electrostatic dissipation and SDT will generally be faster at a higher humidity, while resistivities will generally be lower at a higher humidity.
The gloves of the present invention can be made self releasing by inclusion of a wax during the film forming process. Preferably the wax is carnauba wax. It is preferable that the wax to be used be selected from those that are not likely to induce an allergic reaction in skin that comes in contact therewith. Therefore, food grade waxes are particularly preferred for this application. When used, the waxes are preferably used as an aqueous dispersion at a concentration of from 0.1 to 2 weight percent.
In addition to the conductivity inducing material and the waxes already mentioned, other additives can be included in the gloves of the present invention. Any additive which is known to those of ordinary skill in the art of preparing gloves to be useful can be used with the gloves of the present invention so long as their presence does not degrade the properties of the glove. The additives can also be incorporated into the gloves in any way known to be useful including, but not limited to inclusion in the prepolymer formulation and inclusion in the water used to make the dispersion. For example useful additives include titanium dioxide, calcium carbonate, silicon oxide, defoamers, biocides, and carbon particles.
To make the gloves of the present invention, the polyurethane films used to make the gloves are advantageously applied to a hand-shaped substrate using techniques which are commonly known, such as salt coagulation, thermal coagulation, casting, and combinations
thereof. Coagulation processes are described generally in, for example, Japanese Kokai 2/1/1990, assigned to Daiichi Kogyo Seiyaku K.K., and salt coagulation in particular is generally described in WO 96/08352, assigned to Jackson et al. Preferably, salt coagulation, also referred to herein as "dipping processes" is used to make the gloves of the present invention. A dipping process generally includes the steps of dipping a former into a bath containing a salt coagulant and removing the former; dipping the coagulant-coated former into a bath containing a dispersion of the desired polymer and removing the former; and stripping the resulting film from the former. Typically, the former will be held in air for a period of time after dipping into the polymer, in order to generate gel strength. Also, the former will typically be dipped into a leaching bath such as water before it is cooled and the film is stripped from the former.
The manner of incorporating the conductivity inducing material into the film or glove is not critical. The preferred method for incorporating the conductivity inducing material into the polymer will depend upon the conductivity inducing material used and the polymer used. For example, the conductivity inducing material can be added during the processing of the polymer, during film formation, or by a post-treatment process.
To add the conductivity inducing material to the film or glove during processing of the polymer, when the polymer is polyurethane, the conductivity inducing material can be dissolved in the polyol. The prepolymer is then formed such that the conductivity inducing material is solubilized in the prepolymer mixture. Alternatively, the conductivity inducing material can be added to the polyurethane dispersion after the dispersion is formed.
To add the conductivity inducing material to the film or glove during film formation, when dipping processes are used, a former having thereon a coagulated gel is then dipped into a solution containing the conductivity inducing material. Such dipping preferably occurs after the leaching step but before the film is cured on the former. Preferably, the former is soaked in the conductivity inducing material solution for from 5 to 30 seconds. Such dipping can be performed at room temperature, although higher temperatures can reduce the length of time needed to soak.
To add the conductivity inducing material to the film or glove utilizing a post- treatment process, the cured film is soaked in a solution containing the conductivity
inducing material. Such dipping can occur while the film is still on the former or after the film has been stripped from the former. Preferably, the dipping occurs after the film has been stripped from the former, because all surfaces of the film or glove can be exposed to the salt solution. The length of time required to soak will depend upon the concentration of the salt solution. Preferably, the length of time for the soak is from 1 to 10 minutes. The soak can be performed at room temperature, although higher temperatures can be used and in fact can reduce the amount of soak time required.
The following examples are for illustrative purposes only and are not intended to limit the scope of the claimed invention. Percentages are in weight percents unless otherwise stated.
EXAMPLES
The following materials were used in the examples below:
• Polyether Polyol was a 2000 molecular weight polyoxypropylene diol having 12.5 percent ethylene oxide end capping.
• Low Molecular Weight Diol was a 425 molecular weight all polyoxypropylene diol.
• Polyisocyanate A was MDI having a 4,4' isomer content of 98 percent and an isocyanate equivalent weight of 125.
• Polyisocyanate B was MDI having a 4,4' isomer content of 50 percent and an isocyanate equivalent weight of 125.
• Surfactant was 22 percent solution of sodium dodecyl benzene sulfonate in water.
• Diamine was a 230 molecular weight polyoxypropylene diamine.
• STPB was sodium tetraphenyl boron salt.
• KPF6 was a 0.44M potassium hexafluorophosphate solution in water.
Example 1
A polyurethane prepolymer was prepared by admixing 52.0 parts of Polyether Polyol, 0.33 parts STPB, and 14.7 parts of Low Molecular Weight Diol and then heating the admixture to 50°C. This material was then admixed with 33.3 parts of Polyisocyanate A which had also been warmed to 50°C. A small amount of benzoyl chloride was added to neutralize residual base in the polyols. The admixture was then heated at 70°C for 4 hours and then tested to determine NCO content. The NCO content was 5.75 percent.
A polyurethane dispersion was prepared by admixing 200g of the prepolymer admixed with 13g water and 38g surfactant using a high shear mixer running at about 2500 rpm. Additional water was slowly added until a phase inversion was observed. Additional water was added until the solids content was 23 percent.
A film was then prepared by a coagulation process by heating a steel plate in an oven until it reached a temperature of from 100 to 120°F (38-49°C). The plate was then dipped into a 20 percent solution of calcium nitrate in 1:1 by weight of water and methanol which also included about 1 wt percent of a ethoxylated octylphenol surfactant. The plate was then placed into an oven at 230°F (110°C) for approximately 15 minutes to form a very thin film of calcium nitate on the plate. The plate was allowed to cool to 105°F (40°C) and then dipped into the polyurethane dispersion diluted to 23 percent solids with deionized water and removed (total dwell time is approximately 20 sec). The plate was held for 5 minutes at room temperature to allow the film to generate enough gel strength, followed by leaching in a water bath at 115°F (46°C) for 10 minutes. Both sides of the plate was then sprayed with water at 115°F (40°C) for two additional minutes. The plate was then heated to 230°F (110°C) for 30 minutes and then cooled to ambient temperature. A polyurethane film was peeled from the substrate, conditioned at 12 percent relative humidity and tested for static decay time (SDT) according to Federal Test Method FTMS 101B, method 4046. Results were presented in Table I.
Example 2
Substantially the same procedure as that described in Example 1 was followed, except STPB was not added to the polyether polyol. Instead, after the polyurethane film was
formed, it was post-treated by soaking in KPF6 for 2 minutes. The film was then dried at 80°C for 15 minutes. Test results were presented in Table I.
Example 3
The same procedure as that described in Example 2 was followed. The film was then washed in distilled water for one hour and dried. Test results were presented in Table I.
Example 4
Substantially the same procedure as that described in Example 2 was followed, except that the KPF6 was incorporated during film formation. After the polyurethane film had coagulated to a gel state, it was dipped into KPFfi for 1 minute, then leached for 1 minute, and then dried at 110°C for 45 minutes. Test results were presented in Table I.
Comparative Example 5
Substantially the same procedure as that described in Example 1 was followed, except that no conductivity inducing material was used. Test results were presented in Table I.
Table I
Claims
1. A process for preparing an anti-static film comprising:
incorporating a conductivity inducing material into a polymeric film.
2. The process according to Claim 1 wherein the conductivity inducing material is incorporated during processing of the polymer used to make the polymeric film.
3. The process according to Claim 1 wherein the conductivity inducing material is incorporated during film formation.
4. The process according to Claim 1 wherein the conductivity inducing material is incorporated by a post-treatment process.
5. The process according to Claim 1 wherein the conductivity inducing material is a non-volatile metal salt.
6. The process according to Claim 5 wherein the conductivity inducing material comprises a cation of Li, Be, Na, Mg, Al, K, Ca, Ga, Ge, Cu, Zn, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, b, Sr, In, Sn„ Sb, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Cs, Ba, Tl, Pb, Bi, Po, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Fr, Ra or the Lanthanide series of the Periodic Table of the Elements.
7. The process according to Claim 5 wherein the conductivity inducing material comprises an anion having at least one non-metallic atom of boron, carbon, silicon, phosphorous, arsenic, oxygen, sulfur, selenium, tellarium, fluorine, chlorine, bromine, iodine or astatine.
8. The process according to Claim 1 wherein the polymer is polyurethane, polyolefins, polyvinyl chloride, nitrile rubber, polyisoprene, hydrogenated block copolymers, styrene- isoprene-styrene/styrene-butadiene-styrene block copolymers, styrene butadiene latexes, or natural rubber latex.
9. The process according to Claim 8 wherein the polymer is an aqueous polyurethane dispersion.
10. An anti-static glove prepared according to the process of Claim 1.
11. A process for preparing an anti-static film comprising:
dipping a former into a polymeric dispersion to form a coated former; and
dipping the coated former into a solution comprising a conductivity inducing material.
12. The process according to Claim 11 wherein the former is in the shape of a hand.
13. A process for preparing an anti-static film comprising:
dipping a former into a polymeric dispersion to form a film on the former;
stripping the film from the former; and thereafter
dipping the film into a solution comprising a conductivity inducing material.
14. The process according to Claim 13 wherein the former is in the shape of a hand.
15. A process for preparing an anti-static polyurethane film comprising:
admixing a polyol and a conductivity inducing material to form a polyol mixture;
admixing the polyol mixture with an isocyanate to form a prepolymer;
dispersing the prepolymer in water to form a polyurethane dispersion; and
dipping a former into the polyurethane dispersion to form the anti-static film.
16. The process according to Claim 15 wherein the former is in the shape of a hand.
17. An anti-static film comprising:
a polymeric film; and
a conductivity inducing material incorporated into the film.
18. The anti-static film according to Claim 17, wherein the polymeric film comprises a polymer of polyurethane, polyolefins, polyvinyl chloride, nitrile rubber, polyisoprene, hydrogenated block copolymers, styrene-isoprene-styrene/styrene-butadiene-styrene block copolymers, styrene butadiene latexes, or natural rubber latex.
19. The anti-static film according to Claim 17 wherein the conductivity inducing material is a non- volatile metal salt.
20. The anti-static film according to Claim 19 wherein the conductivity inducing material comprises a cation of Li, Be, Na, Mg, Al, K, Ca, Ga, Ge, Cu, Zn, Sc, Ti, N, Cr, Mn, Fe, Co, Νi, b, Sr, In, Sn„ Sb, Y, Zr, Νb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Cs, Ba, Tl, Pb, Bi, Po, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Fr, Ra or the Lanthanide series of the Periodic Table of the Elements.
21. The anti-static film according to Claim 19 wherein the conductivity inducing material comprises an anion having at least one non-metallic atom of boron, carbon, silicon, phosphorous, arsenic, oxygen, sulfur, selenium, tellarium, fluorine, chlorine, bromine, iodine or astatine.
22. An anti-static glove comprising:
a polymeric film; and
a conductivity inducing material incorporated in the film.
23. The anti-static glove according to Claim 22, wherein the polymeric film comprises a polymer of polyurethane, polyolefins, polyvinyl chloride, nitrile rubber, polyisoprene, hydrogenated block copolymers, styrene-isoprene-styrene/styrene-butadiene-styrene block copolymers, styrene butadiene latexes, or natural rubber latex.
24. The anti-static glove according to Claim 22 wherein the conductivity inducing material is a non- volatile metal salt.
25. The anti-static glove according to Claim 24 wherein the conductivity inducing material comprises a cation of Li, Be, Νa, Mg, Al, K, Ca, Ga, Ge, Cu, Zn, Sc, Ti, N, Cr, Mn, Fe, Co, Νi, b, Sr, In, Sn„ Sb, Y, Zr, Νb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Cs, Ba, Tl, Pb, Bi, Po, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Fr, Ra or the Lanthanide series of the Periodic Table of the Elements.
26. The anti-static glove according to Claim 24 wherein the conductivity inducing material comprises an anion having at least one non-metallic atom of boron, carbon, silicon, phosphorous, arsenic, oxygen, sulfur, selenium, tellarium, fluorine, chlorine, bromine, iodine or astatine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| US20487300P | 2000-05-16 | 2000-05-16 | |
| US204873P | 2000-05-16 | ||
| PCT/US2001/010769 WO2001088024A1 (en) | 2000-05-16 | 2001-04-03 | Polymeric films having anti-static properties |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1326912A1 true EP1326912A1 (en) | 2003-07-16 |
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| EP01924631A Withdrawn EP1326912A1 (en) | 2000-05-16 | 2001-04-03 | Polymeric films having anti-static properties |
Country Status (12)
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|---|---|
| US (1) | US20020002227A1 (en) |
| EP (1) | EP1326912A1 (en) |
| JP (1) | JP2003533573A (en) |
| KR (1) | KR20030046334A (en) |
| CN (1) | CN1441825A (en) |
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| MX (1) | MXPA02011326A (en) |
| NO (1) | NO20025414L (en) |
| NZ (1) | NZ522322A (en) |
| WO (1) | WO2001088024A1 (en) |
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| KR100631792B1 (en) | 2004-07-19 | 2006-10-09 | 호성케멕스 주식회사 | Method for producing antistatic polyurethane gloves using aqueous polyurethane emulsion composition |
| JP2008040810A (en) * | 2006-08-07 | 2008-02-21 | Shin Etsu Polymer Co Ltd | Molded product for RFID system |
| US8110266B2 (en) | 2007-02-08 | 2012-02-07 | Allegiance Corporation | Glove coating and manufacturing process |
| US20080306200A1 (en) | 2007-06-11 | 2008-12-11 | Seong Fong Chen | Antistatic gloves and process for making same |
| CA2716805C (en) | 2008-03-14 | 2017-11-21 | Allegiance Corporation | Water-based resin composition and articles made therefrom |
| US20160183611A1 (en) * | 2013-08-12 | 2016-06-30 | Dipped Products Plc | A latex article with static dissipating property |
| WO2015146334A1 (en) * | 2014-03-26 | 2015-10-01 | Dic株式会社 | Gloves |
| US10863785B2 (en) * | 2016-04-19 | 2020-12-15 | Dic Corporation | Glove |
| AU2018329205B2 (en) * | 2017-09-11 | 2023-03-02 | Skinprotect Corporation Sdn Bhd | Synthetic elastomeric article and methods for producing thereof |
| CN109021323A (en) * | 2018-07-23 | 2018-12-18 | 镇江华扬乳胶制品有限公司 | A kind of antistatic radiation emgloves |
| DE102019118802A1 (en) * | 2019-07-11 | 2021-01-14 | W + R Gmbh | Dissipative glove and method for manufacturing a dissipative glove |
| KR20250050943A (en) * | 2022-08-16 | 2025-04-15 | 안셀 리미티드 | Anti-static Dissipative Protective Gloves |
| CN116041770B (en) * | 2022-11-04 | 2024-09-03 | 宁波东旭成新材料科技有限公司 | Preparation method of antistatic polyester film |
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| US4459352A (en) * | 1982-12-27 | 1984-07-10 | Eastman Kodak Company | Conductive coating composition and composite bases and elements containing same |
| US4542095A (en) * | 1984-07-25 | 1985-09-17 | Eastman Kodak Company | Antistatic compositions comprising polymerized alkylene oxide and alkali metal salts and elements thereof |
| JP3242683B2 (en) * | 1991-11-27 | 2001-12-25 | 有限会社ユーエムエス | Plastic surface treatment agent and treatment method |
| JPH05311022A (en) * | 1992-05-11 | 1993-11-22 | Du Pont Mitsui Polychem Co Ltd | Polyvinyl chloride composition |
| US5472639A (en) * | 1993-08-13 | 1995-12-05 | The Dow Chemical Company | Electroconductive foams |
| JPH0770556A (en) * | 1993-08-31 | 1995-03-14 | Nippon Oil & Fats Co Ltd | Coatable antistatic agent composition |
-
2001
- 2001-04-03 US US09/824,640 patent/US20020002227A1/en not_active Abandoned
- 2001-04-03 KR KR1020027015230A patent/KR20030046334A/en not_active Withdrawn
- 2001-04-03 AU AU2001251271A patent/AU2001251271A1/en not_active Abandoned
- 2001-04-03 JP JP2001585239A patent/JP2003533573A/en active Pending
- 2001-04-03 EP EP01924631A patent/EP1326912A1/en not_active Withdrawn
- 2001-04-03 NZ NZ522322A patent/NZ522322A/en not_active Application Discontinuation
- 2001-04-03 MX MXPA02011326A patent/MXPA02011326A/en unknown
- 2001-04-03 BR BR0111164-7A patent/BR0111164A/en not_active Application Discontinuation
- 2001-04-03 CN CN01809274A patent/CN1441825A/en active Pending
- 2001-04-03 CA CA002409140A patent/CA2409140A1/en not_active Abandoned
- 2001-04-03 WO PCT/US2001/010769 patent/WO2001088024A1/en not_active Ceased
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2002
- 2002-11-12 NO NO20025414A patent/NO20025414L/en not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0188024A1 * |
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| KR20030046334A (en) | 2003-06-12 |
| NZ522322A (en) | 2004-03-26 |
| JP2003533573A (en) | 2003-11-11 |
| BR0111164A (en) | 2003-04-15 |
| AU2001251271A1 (en) | 2001-11-26 |
| NO20025414L (en) | 2003-01-15 |
| WO2001088024A1 (en) | 2001-11-22 |
| NO20025414D0 (en) | 2002-11-12 |
| CA2409140A1 (en) | 2001-11-22 |
| CN1441825A (en) | 2003-09-10 |
| US20020002227A1 (en) | 2002-01-03 |
| MXPA02011326A (en) | 2004-09-06 |
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